Fungicide mixtures

ABSTRACT

Fungicidal mixtures, comprising 
     a) an oxime ether of the formula I ##STR1## where the substituents have the following meanings: X is oxygen or amino (NH); 
     Y is CH or N; 
     Z is oxygen, sulfur, amino (NH) or C 1  -C 4  -alkylamino (N--C 1  -C 4  -alkyl); 
     R&#39; is C 1  -C 6  -alkyl, C 1  -C 6  -haloalkyl, C 3  -C 6  -alkenyl, C 2  -C 6  -haloalkenyl, C 3  -C 6  -alkynyl, C 3  -C 6  -haloalkynyl, C 3  -C 6  -Cycloalkylmethyl, or is benzyl which can be partially or fully halogenated and/or can have attached to it one to three of the following radicals: cyano, C 1  -C 4  -alkyl, C 1  -C 4  -haloalkyl, C 1  -C 4  -alkoxy, C 1  -C 4  -haloalkoxy and C 1  -C 4  -alkylthio and/or 
     b) a carbamate of the formula II ##STR2## where T is CH or N, n is 0, 1 or 2 and R is halogen, C 1  -C 4  -alkyl or C 1  -C 4  -haloalkyl, it being possible for the radicals R to be different when n is 2, and 
     c) a pyrimidine derivative of the formula III ##STR3## where R is methyl, propyn-1-yl or cyclopropyl, in a synergistically active amount.

This application is a 371 of PCT/EP97/02023, filed Apr. 22, 1997.

The present invention relates to a fungicidal mixture which comprises

a) an oxime ether of the formula I ##STR4## where the substituents havethe following meanings: X is oxygen or amino (NH);

Y is CH or N;

Z is oxygen, sulfur, amino (NH) or C₁ -C₄ -alkylamino (N--C₁ -C₄-alkyl);

R' is C₁ -C₆ -alkyl, C₁ -C₆ -haloalkyl, C₃ -C₆ -alkenyl, C₂ -C₆-haloalkenyl, C₃ -C₆ -alkynyl, C₃ -C₆ -haloalkynyl, C₃ -C₆-cycloalkylmethyl, or is benzyl which can be partially or fullyhalogenated and/or can have attached to it one to three of the followingradicals: cyano, C₁ -C₄ -alkyl, C₁ -C₄ -haloalkyl, C₁ -C₄ -alkoxy, C₁-C₄ -haloalkoxy and C₁ -C₄ -alkylthio and/or

b) a carbamate of the formula II ##STR5## where T is CH or N, n is 0, 1or 2 and R is halogen, C₁ -C₄ -alkyl or C₁ -C₄ -haloalkyl, it beingpossible for the radicals R to be different when n is 2, and

c) a pyrimidine derivative of the formula III ##STR6## where R ismethyl, propyn-1-yl or cyclopropyl, in a synergistically active amount.

Moreover, the invention relates to methods of controlling harmful fungiwith the compounds I and/or II and III or synergistic mixturescomprising them, and to the use of the compounds I and/or II and thecompounds III, respectively, for the preparation of such mixtures.

The compounds of the formula I, their preparation and their actionagainst harmful fungi have been disclosed in the literature (WO-A95/21,153, WO-A 95/21,154, DE-A 195 28 651.0).

Compounds of the formula II, their preparation and their action againstharmful fungi have been described in WO-A 96/01,256 and WO-A 01,258.

The pyrimidine derivatives III, their preparation and their actionagainst harmful fungi have also been disclosed [R=methyl: DD-A 151 404(common name: pyrimethanil); R=1-propynyl: EP-A 224 339 (common name:mepanipyrim); R=cyclopropyl: EP-A 310 550].

It was an object of the present invention to provide mixtures which havean improved activity gainst harmful fungi combined with a reduced totalamount of active ingredients applied (synergistic mixtures) with a viewto reducing the rates of application and to improving the spectrum ofaction of the known compounds.

Accordingly, we have found that this object is achieved by the mixturedefined at the outset. Moreover, we have found that better control ofthe harmful fungi is possible by applying the compounds I and/or II andthe compounds III simultaneously together or separately or by applyingthe compounds I and/or II and the compounds III in succession than whenjust the compounds I and/or II or III are used.

In particular, the general formula I represents oxime ethers in which Xis oxygen and Y is CH or X is amino and Y is N.

Moreover, preferred compounds I are those where Z is oxygen.

Equally, preferred compounds I are those where R' is alkyl or benzyl.

Especially preferred with a view to their use in the synergisticmixtures according to the invention are the compounds I compiled in thetables which follow:

Table 1.

Compounds of the formula IA where ZR' for each compound corresponds toone line of Table A ##STR7##

Table 2.

Compounds of the formula IB where ZR' for each compound corresponds toone line of Table A ##STR8##

                  TABLE A                                                         ______________________________________                                        No.            ZR'                                                            ______________________________________                                        I.1            O--CH.sub.2 CH.sub.2 CH.sub.3                                    I.2 O--CH(CH.sub.3).sub.2                                                     I.3 O--CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                    I.4 O--CH(CH.sub.3)CH.sub.2 CH.sub.3                                          I.5 O--CH.sub.2 CH(CH.sub.3).sub.2                                            I.6 O--C(CH.sub.3).sub.3                                                      I.7 S--C(CH.sub.3).sub.3                                                      I.8 O--CH(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3                                 I.9 O--CH.sub.2 C(CH.sub.3).sub.3                                             I.10 O--CH.sub.2 C(Cl)═CCl.sub.2                                          I.11 O--CH.sub.2 CH═CH--Cl (trans)                                        I.12 O--CH.sub.2 C(CH.sub.3)═CH.sub.2                                     I.13 O--CH.sub.2 -(cyclopropyl)                                               I.14 O--CH.sub.2 --C.sub.6 H.sub.5                                            I.15 O--CH.sub.2 --[4-F--C.sub.6 H.sub.4 ]                                    I.16 O--CH.sub.2 CH.sub.3                                                     I.17 O--CH(CH.sub.2 CH.sub.3).sub.2                                         ______________________________________                                    

In relation to the C═Y double bond, the compounds of the formula I canbe in the E or the Z configuration (in relation to the carboxylic acidfunction). Accordingly, they can be used in the mixture according to theinvention in each case either in the form of pure isomers or else in theform of an E/Z isomer mixture. The E/Z isomer mixture or the E isomerare preferably used in each case, the E isomer being especiallypreferred in many cases.

The C═N double bonds of the oxime ether groups in the side chain of thecompounds I can be in each case in the form of pure E or Z isomers or inthe form of E/Z isomer mixtures. The compounds I can be used in themixtures according to the invention as isomer mixtures or else as pureisomers. With a view to their use, compounds I which are particularlypreferred are those where the terminal oxime ether group of the sidechain is in the cis configuration (OCH₃ group relative to ZR').

In particular, the formula II represents carbamates where thecombination of the substituents corresponds to one line of the tablewhich follows:

                  TABLE 3                                                         ______________________________________                                        No.       T               R.sub.n                                             ______________________________________                                        II.1      N               2-F                                                   II.2 N 3-F                                                                    II.3 N 4-F                                                                    II.4 N 2-Cl                                                                   II.5 N 3-Cl                                                                   II.6 N 4-Cl                                                                   II.7 N 2-Br                                                                   II.8 N 3-Br                                                                   II.9 N 4-Br                                                                   II.10 N 2-CH.sub.3                                                            II.11 N 3-CH.sub.3                                                            II.12 N 4-CH.sub.3                                                            II.13 N 2-CH.sub.2 CH.sub.3                                                   II.14 N 3-CH.sub.2 CH.sub.3                                                   II.15 N 4-CH.sub.2 CH.sub.3                                                   II.16 N 2-CH(CH.sub.3).sub.2                                                  II.17 N 3-CH(CH.sub.3).sub.2                                                  II.18 N 4-CH(CH.sub.3).sub.2                                                  II.19 N 2-CF.sub.3                                                            II.20 N 3-CF.sub.3                                                            II.21 N 4-CF.sub.3                                                            II.22 N 2,4-F.sub.2                                                           II.23 N 2,4-Cl.sub.2                                                          II.24 N 3,4-Cl.sub.2                                                          II.25 N 2-Cl, 4-CH.sub.3                                                      II.26 N 3-Cl, 4-CH.sub.3                                                      II.27 CH 2-F                                                                  II.28 CH 3-F                                                                  II.29 CH 4-F                                                                  II.30 CH 2-Cl                                                                 II.31 CH 3-Cl                                                                 II.32 CH 4-Cl                                                                 II.33 CH 2-Br                                                                 II.34 CH 3-Br                                                                 II.35 CH 4-Br                                                                 II.36 CH 2-CH.sub.3                                                           II.37 CH 3-CH.sub.3                                                           II.38 CH 4-CH.sub.3                                                           II.39 CH 2-CH.sub.2 CH.sub.3                                                  II.40 CH 3-CH.sub.2 CH.sub.3                                                  II.41 CH 4-CH.sub.2 CH.sub.3                                                  II.42 CH 2-CH(CH.sub.3).sub.2                                                 II.43 CH 3-CH(CH.sub.3).sub.2                                                 II.44 CH 4-CH(CH.sub.3).sub.2                                                 II.45 CH 2-CF.sub.3                                                           II.46 CH 3-CF.sub.3                                                           II.47 CH 4-CF.sub.3                                                           II.48 CH 2,4-F.sub.2                                                          II.49 CH 2,4-Cl.sub.2                                                         II.50 CH 3,4-Cl.sub.2                                                         II.51 CH 2-Cl, 4-CH.sub.3                                                     II.52 CH 3-Cl, 4-CH.sub.3                                                   ______________________________________                                    

The compounds II.12, II.23; II.32 and II.38 are especially preferred.

Due to the basic character, the compounds of the formulae I to III arecapable of forming salts with inorganic or organic acids or with metalions.

Examples of inorganic acids are hydrohalic acids such as hydrofluoricacid, hydrochloric acid, hydrobromic acid and hydroiodic acid, sulfuricacid, phosphoric acid and nitric acid.

Suitable organic acids are, for example, formic acid, carboxylic acidand alkanoic acids such as acetic acid, trifluoroacetic acid,trichloroacetic acid and propionic acid, and also glycolic acid,thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid,cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids havingstraight-chain or branched alkyl radicals having from 1 to 20 carbonatoms), arylsulfonic acids or -disulfonic acids (aromatic radicals suchas phenyl and naphthyl which have attached to them one or two sulfogroups), alkylphosphonic acids (phosphonic acids having straight-chainor branched alkyl radicals of from 1 to 20 carbon atoms), arylphosphonicacids or -diphosphonic acids (aromatic radicals such as phenyl andnaphthyl which have attached to them one or two phosphonic acidradicals), it being possible for the alkyl or aryl radicals to haveattached to them further substituents, eg. p-toluenesulfonic acid,salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid,2-acetoxybenzoic acid etc.

Suitable metal ions are, in particular, the ions of the elements of thesecond main group, in particular calcium and magnesium, and of the thirdand fourth main group, in particular aluminum, tin and lead, and of thefirst to eighth sub-group, in particular chromium, manganese, iron,cobalt, nickel, copper, zinc and others. Especially preferred are themetal ions of the elements of the sub-groups of the fourth period. Themetals can in this case be in the various valences which they canassume.

When preparing the mixtures, it is preferred to employ the pure activeingredients, with which further active ingredients against harmful fungior other pests such as insects, arachnids or nematodes, or elseherbicidal or growth-regulating active ingredients or fertilizers can beadmixed, if so desired.

The mixtures of the compounds I and/or II and III, or the simultaneousjoint or separate use of the compounds I and/or II and III, aredistinguished by an outstanding activity against a broad spectrum ofphytopathogenic fungi, in particular from the classes of theAscomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some ofthem act systemically and can therefore be employed as foliar- andsoil-acting fungicides.

They are especially important for controlling a large number of fungi ina variety of crop plants such as cotton, vegetable species (eg.cucumbers, beans and curcubits), barley, grass, oats, coffee, maize,fruit species, rice, rye, soybeans, grapevine, wheat, ornamentals, sugarcane, and a variety of seeds.

They are particularly suitable for controlling the followingphytopathogenic fungi: Erysiphe graminis (powdery mildew) on cereals,Erysiphe cichoracearum and Sphaerotheca fuliginea on curcubits,Podosphaera leucotricha on apples, Uncinula necator on grapevines,Puccinia species on cereals, Rhizoctonia species on cotton, rice andlawn, Ustilago species on cereals and sugar cane, Venturia inaequalis(scab) on apples, Helminthosporium species on cereals, Rhynchosporiumsecalis, Septoria nodorum on wheat, Botrytis cinerea (gray mold) onstrawberries, vegetables, ornamentals and grapevines, Cercosporaarachidicola on peanuts, Pseudocercosporella herpotrichoides on wheatand barley, Pyricularia oryzae on rice, Phytophthora infestans onpotatoes and tomatoes, Plasmopara viticola on grapevines, Alternariaspecies on vegetables and fruit, and Fusarium and Verticillium species.

Furthermore, they can be used in the protection of materials (eg. in theprotection of wood), for example against Paecilomyces variotii.

The compounds I and/or II and III can be applied simultaneously togetheror separately or in succession, the sequence, in the case of separateapplication, generally not having any effect on the result of thecontrol measures.

The compounds I and/or II and III are normally used in a weight ratio offrom 20:1 to 0.1:2, preferably 10:1 to 0.1:1, in particular 5:1 to0.2:1.

The application rates of the mixtures according to the invention arefrom 0.01 to 3 kg/ha, preferably 0.1 to 1.5 kg/ha, in particular 0.4 to1.0 kg/ha, depending on the nature of the desired effect.

In the case of the compounds I and/or II, the application rates are ingeneral from 0.01 to 0.5 kg/ha, preferably 0.05 to 0.5 kg/ha, inparticular 0.05 to 0.2 kg/ha.

Correspondingly, in the case of the compounds III, the application ratesare normally from 0.1 to 1.0 kg/ha, preferably 0.4 to 1.0 kg/ha, inparticular 0.4 to 0.8 kg/ha.

For seed treatment, the application rates of the mixture are generallyfrom 0.001 to 50 g/kg seed, preferably 0.01 to 10 g/kg, in particular0.01 to 8 g/kg.

If phytopathogenic harmful fungi are to be controlled, the separate orjoint application of the compounds I and II or of the mixtures of thecompounds I and/or II and III is effected by spraying or dusting theseeds, the plants or the soils before or after sowing of the plants, orbefore or after plant emergence.

The fungicidal synergistic mixtures according to the invention, or thecompounds I and/or II and III, can be formulated for example in the formof ready-to-spray solutions, powders and suspensions or in the form ofhighly concentrated aqueous, oily or other suspensions, dispersions,emulsions, oil dispersions, pastes, dusts, materials for spreading orgranules, and applied by spraying, atomizing, dusting, spreading orpouring. The use form depends on the intended purpose; in any case, itshould guarantee as fine and uniform as possible a distribution of themixture according to the invention.

The formulations are prepared in a manner known per se, eg. by addingsolvents and/or carriers. It is usual to admix inert additives, such asemulsifiers or dispersants, with the formulations.

Suitable surfactants are the alkali metal salts, alkaline earth metalsalts and ammonium salts of aromatic sulfonic acids, eg. ligno-,phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fattyacids, of alkyl- and alkylarylsulfonates, of alkyl, lauryl ether andfatty alcohol sulfates, and salts of sulfated hexa-, hepta- andoctadecanols or fatty alcohol glycol ethers, condensates of sulfonatednaphthalene and its derivatives with formaldehyde, condensates ofnaphthalene, or of the naphthalenesulfonic acids, with phenol andformaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctyl-,octyl- or nonylphenol, alkylphenyl polyglycol ethers or tributylphenylpolyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol,fatty alcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene or polyoxypropylene alkyl ethers, lauryl alcoholpolyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquorsor methylcellulose.

Powders, materials for spreading and dusts can be prepared by mixing orjointly grinding the compounds I and/or II and III or the mixture of thecompounds I and/or II and III with a solid carrier.

Granules (eg. coated granules, impregnated granules or homogeneousgranules) are normally prepared by binding the active ingredient, oractive ingredients, to a solid carrier.

Fillers or solid carriers are, for example, mineral earths such assilica gel, silicas, silicates, talc, kaolin, limestone, lime, chalk,bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,magnesium sulfate, magnesium oxide, ground synthetic materials, andfertilizers such as ammonium sulfate, ammonium phosphate, ammoniumnitrate, ureas, and products of vegetable origin such as cereal meal,tree bark meal, wood meal and nutshell meal, cellulose powders or othersolid carriers.

The formulations generally comprise from 0.1 to 95% by weight,preferably 0.5 to 90% by weight, of one of the compounds I and/or II orIII, or of the mixture of the compounds I and/or II and III. The activeingredients are employed in a purity of from 90% to 100%, preferably 95%to 100% (according to NMR spectrum or HPLC).

The compounds I and/or II or III, or the mixtures, or the correspondingformulations, are applied by treating the harmful fungi or the plants,seeds, soils, areas, materials or spaces to be kept free from them witha fungicidally active amount of the mixture, or of the compounds Iand/or II and III in the case of separate application. Application canbe effected before or after infection by the harmful fungi.

The fungicidal activity of the compounds and of the mixtures wasdemonstrated by the following experiments:

The active ingredients, separately or together, are formulated as a 10%emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weightof Nekanil® LN (Lutensol® AP6, wetting agent having emulsifying anddispersing action based on ethoxylated alkylphenols) and 10% by weightof Emulphor® EL (Emulan® EL, emulsifier based on ethoxylated fattyalcohols) and diluted with water to give the desired concentration.

Evaluation is carried out by determining the infected leaf areas inpercent. These percentages are converted into efficacies. The expectedefficacies of the mixtures of the active ingredients are determinedusing Colby's formula [R. S. Colby, Weeds 15, 20-22 (1967)] and comparedwith the observed efficacies.

Colby's formula:

    E=x+y-x·y/100

E expected efficacy, expressed in % of the untreated control, when usingthe mixture of the active ingredients A and B at concentrations of a andb

x efficacy, expressed in % of the untreated control, when using activeingredient A at a concentration of a

y efficacy, expressed in % of the untreated control, when using activeingredient B at a concentration of b

The efficacy (W) is calculated as follows using Abbot's formula:

    W=(1-α)·100/β

α is the fungal infection of the treated plants in % and

β is the fungal infection of the untreated (control) plants in %

An efficacy of 0 means that the infection level of the treated plantscorresponds to that of the untreated control plants; an efficacy of 100means that the treated plants are not infected.

EXAMPLES 1-17 Protective Activity Against Puccinia recondita on Wheat(Leaf Rust on Wheat)

Leaves of wheat seedlings cv. "Fruhgold" in pots were sprayed to run-offwith an aqueous spray mixture which had been prepared with a stocksolution of 10% active ingredient, 63% cyclohexanone and 27% emulsifier.The next day, the leaves were moistened and dusted with leaf rust spores(Puccinia recondita). The pots were subsequently placed for 24 hoursinto a chamber with high atmospheric humidity (90 to 95%) at from 20 to22° C. During this time, the spores germinated, and the germinationtubes penetrated the plant tissue for a further 7 days at from 20 to 22°C. and a relative atmospheric humidity of from 65 to 70%. The extent ofrust development on the leaves was then determined visually.

The visually determined values for the percentage of infected leaf areawere transformed into efficacy in percent of the untreated control. Anefficacy of 0 is the same infection level as in the untreated control,an efficacy of 100 is an infection level of 0%. The expected efficaciesfor combinations of active ingredients were calculated using Colby'sformula (Colby, S. R. (Calculating synergistic and antagonisticresponses of herbicide Combinations", Weeds, 15, p. 20-22, 1967) andcompared with the observed efficacies.

                  TABLE 4                                                         ______________________________________                                                       Active ingredient                                                 concentration in Efficacy in % of                                            Active ingredient or the spray mixture the untreated                          combination in ppm control                                                  ______________________________________                                        1V   Control (untreated)                                                                         (Infection level                                                                          0                                                  100%)                                                                       2V Table 1 A No. 2 = A 12.5 40                                                  5 10                                                                          2.5 0                                                                       3V Table 1 A No. 4 = B 5 80                                                     2.5 20                                                                      4V III a 125 50                                                                R = methyl 50 20                                                              pyrimethanil 25 0                                                            5V III b 125 0                                                                 R = 1-propynyl 50 0                                                           mepanipyrim 25 0                                                             6V III c 50 85                                                                 R = cyclopropyl                                                               cyprodinil                                                                 ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                               Active ingredient concen-                                                 tration in the spray mix- Observed Calculated                                Ex. ture in ppm efficacy efficacy*)                                         ______________________________________                                        7      12.5 A +         90       70                                              12.5 IIIa                                                                    8 5 A + 80 28                                                                  50 IIIa                                                                      9 2.5 A + 20 0                                                                 25 IIIa                                                                      10 12.5 A + 97 40                                                              125 IIIb                                                                     11 5 A + 90 10                                                                 50 IIIb                                                                      12 2.5 A + 30 0                                                                25 IIIb                                                                      13 5 A + 95 87                                                                 50 IIIc                                                                      14 5 B + 80 68                                                                 50 IIIa                                                                      15 5 B + 90 60                                                                 50 IIIb                                                                      16 2.5 B + 80 20                                                               50 IIIb                                                                      17 5 B + 100 94                                                                50 IIIc                                                                    ______________________________________                                         *)calculated using Colby's formula                                       

The test results reveal that for all mixing ratios the observed efficacyexceeds the efficacy precalculated using Colby's formula.

EXAMPLES 18-34 Protective Activity Against Puccinia recondita on Wheat(Leaf Rust of Wheat)

Leaves of wheat seedlings cv. "Fruhgold" in pots were sprayed to run-offwith an aqueous spray mixture which had been prepared with a stocksolution of 10% active ingredient, 63% cyclohexanone and 27% emulsifier.The next day, the leaves were moistened and dusted with leaf rust spores(Puccinia recondita). The pots were subsequently placed for 24 hoursinto a chamber with high atmospheric humidity (90 to 95%) at from 20 to22° C. During this time, the spores germinated, and the germinationtubes penetrated the plant tissue. The treated and infected plants werethen grown in the greenhouse for a further 7 days at from 20 to 22° C.and a relative atmospheric humidity of 65 to 70%. The extent of rustdevelopment on the leaves was then determined visually.

The visually determined values for the percentage of infected leaf areawere transformed into efficacy in percent of the untreated control. Anefficacy of 0 is the same infection level as in the untreated control,an efficacy of 100 is an infection level of 0%. The expected efficaciesfor combinations of active ingredients were calculated using Colby'sformula (Colby, S. R. (Calculating synergistic and antagonisticresponses of herbicide Combinations", Weeds, 15, p. 20-22, 1967) andcompared with the observed efficacies.

                  TABLE 6                                                         ______________________________________                                                           Active ingredient                                                                           Efficacy                                        Active ingredient or concentration in the in % of the                        Ex. combinations spray mixture in ppm untreated control                     ______________________________________                                        18V  Control (untreated)                                                                         (Infection level                                                                            0                                                100%)                                                                       19V Compound No. II.32 12.5 85                                                 of Table 3 = C 5 80                                                            2.5 60                                                                        1.25 10                                                                     20V Compound No. II.38 12.5 90                                                 of Table 3 = D 5 80                                                            2.5 20                                                                      21V IIIa 125 50                                                                R = methyl 50 20                                                              pyrimethanil 25 0                                                            22V III b 125 0                                                                R = 1-propynyl 50 0                                                           mepanipyrim 25 0                                                               12.5 0                                                                      23V IIIc 12.5 0                                                                R = cyclopropyl                                                               cyprodinil                                                                 ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                               Active ingredient con-                                                    centration in the spray Observed Calculated                                  Ex. mixture in ppm efficacy efficacy*)                                      ______________________________________                                        24     12.5 C +        97       93                                               125 IIIa                                                                     25 5 C + 95 84                                                                 50 IIIa                                                                      26 2.5 C + 95 60                                                               25 IIIa                                                                      27 5 C + 90 80                                                                 50 IIIb                                                                      28 2.5 C + 85 60                                                               25 IIIb                                                                      29 1.25 C + 40 10                                                              12.5 IIIb                                                                    30 12.5 + 100 95                                                               125 IIIa                                                                     31 12.5 D + 100 90                                                             125 IIIb                                                                     32 5 D + 97 80                                                                 50 IIIb                                                                      33 2.5 D + 80 20                                                               25 IIIb                                                                      34 2.5 D + 93 20                                                               12,5 IIIb                                                                    35 2.5 D + 70 20                                                               12.5 IIIc                                                                  ______________________________________                                         *)calculated using Colby's formula                                       

The examples of Examples 1-34 reveal that for all mixing ratios theobserved efficacy exceeds the value precalculated using Colby's formula.

We claim:
 1. A fungicidal composition comprising synergisticallyeffective amounts ofb) a carbamate of formula II ##STR9## wherein T isCH or N, n is 0, 1 or 2, R is halogen, C₁ -C₄ -alkyl or C₁ -C₄-haloalkyl, and the radicals R are identical or different when n is 2,and c) a pyrimidine compound of formula III ##STR10## wherein R ismethyl, propyn-1-yl or cyclopropyl.
 2. The fungicidal compositiondefined in claim 1, comprising the carbamate and the compound of formulaIII in a weight ratio of from 20:1 to 0.1:2.
 3. The fungicidalcomposition defined in claim 1, wherein T is CH, n is 1 and R is 4-Cl.4. The fungicidal composition defined in claim 1, wherein R is methyl.5. The fungicidal composition defined in claim 1, further comprising anoxime ether of formula I ##STR11## wherein X is oxygen or NH;Y is CH orN; Z is oxygen, sulfur, NH or C₁ -C₄ -alkylamino; and R' is C₁ -C₆-alkyl, C₁ -C₆ -haloalkyl, C₃ -C₆ -alkenyl, C₂ -C₆ -haloalkenyl, C₃ -C₆-alkynyl, C₃ -C₆ -haloalkynyl, C₃ -C₆ -cycloalkylmethyl, or is benzylwhich is unsubstituted, partially or fully halogenated and/or carriesfrom one to three of the following radicals: cyano, C₁ -C₄ -alkyl, C₁-C₄ -haloalkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkoxy and C₁ -C₄-alkylthio.
 6. The fungicidal composition defined in claim 5, comprising(i) the carbamate and/or the oxime ether and (ii) the compound offormula III in a weight ratio of from 20:1 to 0.1:2.
 7. The fungicidalcomposition defined in claim 5, wherein T is CH, n is 1 and R is 4-Cl.8. The fungicidal composition defined in claim 5, wherein R is methyl.9. A method of controlling harmful fungi, which comprises treating theharmful fungi, their environment, or plants, seeds, soils, areas,materials or spaces which are to be kept free from said fungi withsynergistically effective amounts of the carbamate and the compound offormula III defined in claim
 1. 10. The method defined in claim 9,wherein the carbamate and the compound of formula III are appliedsimultaneously together or separately or in succession.
 11. The methoddefined in claim 9, wherein the carbamate and the compound III areapplied in a weight ratio of from 20:1 to 0.1:2.
 12. The method definedin claim 9, wherein the carbamate is applied in an amount of from 0.01to 0.5 kg/ha.
 13. The method defined in claim 9, wherein the compound offormula III is applied in an amount of from 0.1 to 1.0 kg/ha.
 14. Themethod defined in claim 9, wherein T is CH, n is 1 and R is 4-Cl. 15.The method defined in claim 9, wherein R is methyl.
 16. A method ofcontrolling harmful fungi, which comprises treating the harmful fungi,their environment, or plants, seeds, soils, areas, materials or spaceswhich are to be kept free from said fungi with synergistically effectiveamounts of the carbamate, the oxime ether and the compound of formulaIII defined in claim
 5. 17. The method defined in claim 16, wherein thecarbamate and the compound of formula III are applied simultaneouslytogether or separately or in succession.
 18. The method defined in claim16, wherein (i) the carbamate and/or the oxime ether and (ii) thecompound of formula III are applied in a weight ratio of from 20:1 to0.1:2.
 19. The method defined in claim 16, wherein the carbamate isapplied in an amount of from 0.01 to 0.5 kg/ha.
 20. The method definedin claim 16, wherein the oxime ether is applied in an amount of from0.01 to 0.5 kg/ha.
 21. The method defined in claim 16, wherein thecompound of formula III is applied in an amount of from 0.1 to 1.0kg/ha.
 22. The method defined in claim 16, wherein T is CH, n is 1 and Ris 4-Cl.
 23. The method defined in claim 16, wherein R is methyl.